DE10128900A1 - Cationically surface-modified hydrophilic non-crosslinked homo- or co-polymer nanoparticles are used as an aqueous dispersion in stain-release treatment of textile or non-textile surfaces - Google Patents

Abstract

Cationically surface-modified hydrophilic non-crosslinked homo or co-polymer nanoparticles are claimed, as is also stain-release treatment of textile or non-textile surfaces using aqueous dispersions of the particles. INDEPENDENT CLAMS are included for: (1) cationically-modified hydrophilic non-crosslinked polymer nanoparticles of size 10 nm to 2 microns which are surface-coated with cationic polymers, polyvalent metal ions or cationic surfactants, the crosslinked polymer comprising (by wt.) (a) carboxyl group-containing ethylenically-unsaturated monomers or salts (60-100%); (b) water-insoluble mono- ethylenically-unsaturated monomers (0-40%); (c) sulfonic- and/or phosphonic-acid-containing monomers (0-25%); and (d) water-soluble nonionic monomers (0-30%); (2) aqueous dispersions of such particles, the dispersions being stabilized with anionic, nonionic and/or betaine-type surfactants and/or protective colloids; and (3) stain-releasing treatment of textile or non-textile surfaces using the dispersions.

Description

The invention relates to a method for the treatment of dirt removal Surfaces of textile and non-textile materials using cationically modified hydrophilic nanoparticles, the cationically modified hydrophilic nanoparticles themselves, aqueous dispersions containing them, the use of the hydrophilic nanoparticles and the cationically modified hydrophilic nanoparticles as a dirt-removing additive for dishwashing, care, washing and cleaning agents as well as dirt-removing agents solution-promoting treatment of surfaces.

Dispersions of particles of hydrophobic polymers, especially aqueous dispersions of synthetic polymers and waxes are used in the art to to modify the properties of surfaces. For example, one uses aqueous dispersions of finely divided hydrophobic polymers as binders in Paper coating slips for coating paper or as a coating material. The each on a substrate using common methods, e.g. B. by knife, brush, watering or Impregnated applied dispersions are dried. Filming the dispers distributed particles on the respective surface to form a coherent film.

Aqueous washing, rinsing, cleaning and care processes, on the other hand, are common performed in a highly diluted fleet, the ingredients of each Most of the formulation used does not remain on the substrate, but rather rather be disposed of with the wastewater. The modification of surfaces with dispersed hydrophobic particles only succeed in the processes mentioned above completely unsatisfactory. For example, from US-A-3 580 853 Detergent formulation known that a water-insoluble fine-particle substance such as Contains biocides and certain cationic polymers that cause deposition and retention increase the biocides on the surfaces of the laundry.  

From US-A-3 993 830 it is known to use a non-permanent finish Apply dirt repellency to a textile good by using the textile good treated with a dilute aqueous solution containing a polycarboxylate and a contains water-soluble salt of a polyvalent metal. Coming as polycarboxylates preferably water-soluble copolymers of ethylenically unsaturated Monocarboxylic acids and alkyl acrylates into consideration. The mixtures are used in the Textile laundry used in the household in the washing machine rinse cycle.

From US-A-3782898 it is known to use a non-permanent finish Apply dirt repellency to a textile good by using the textile good treated with an acidic dilute aqueous solution containing an acrylate polymer in solution or emulsified form. The writing contains no indication of an advantageous Use of particulate polymers and in particular no reference to one advantageous combination of particulate polymers with cationic substances.

The present invention has for its object to provide an improved method Modification of textile surfaces, leather, hard to promote dirt release to provide smooth surfaces and hard porous surfaces.

The object is achieved according to the invention by a process for the dirt-removing treatment of surfaces of textile and non-textile materials, in which cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

• a) 60 to 100 wt .-% of one or more carboxyl-containing ethylenically unsaturated monomers or their salts,
• b) 0 to 40% by weight of one or more water-insoluble monoethylenic unsaturated monomers,
• c) 0 to 25 wt .-% of one or more sulfonic and / or phosphonic acid group-containing monomers or their salts,
• d) 0 to 30% by weight of one or more water-soluble nonionic monomers

are applied to the surface of the materials from an aqueous dispersion, the dispersion of the hydrophilic nanoparticles with anionic, nonionic and / or betaine emulsifiers and / or protective colloids can be stabilized, and wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 microns and by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants are cationically modified.

The object is further achieved by using the hydrophilic nanoparticles and the cationically modified hydrophilic nanoparticles and the hydrophilic or aqueous dispersions containing cationically modified hydrophilic nanoparticles as a dirt-removing additive to dishwashing, care, washing and cleaning agents.

The invention also relates to the cationically modified hydrophilic Nanoparticles themselves and the aqueous dispersions containing them.

Hydrophilic nanoparticles in the sense of the present invention are hydrophilic Polymer particles from uncrosslinked polymers or particulate hydrogels from crosslinked Polymers whose particle size is 10 nm to 2 µm and which are cationic Components can be bound to the surface to be modified. As particulate hydrogels are polymer particles that are heavily swollen with water, the acidic groups of the polymer particles with water-soluble bases such as LiOH, NaOH, KOH or ammonium hydroxides are partially neutralized. As a cationic Components are cationic polymers, polyvalent metal cations or cationic Suitable for surfactants. Cationically modified hydrophilic nanoparticles in the sense of the invention have an assignment of their surface with one or more of the above cationic components.

The hydrophilic nanoparticles to be used according to the invention are used in the Production initially obtained in the form of aqueous dispersions and can, if appropriate after concentration or dilution, are used as such. The hydrophilic After spray drying, nanoparticles can also be obtained and used as a solid become. From the aqueous dispersions of the hydrophilic nanoparticles can by Addition of the cationic component to aqueous dispersions of the cationically modified Obtained hydrophilic nanoparticles and used as such or after Spray drying the cationically modified hydrophilic nanoparticles as a solid  preserved and used. The cationically modified hydrophilic nanoparticles can also only be used under the conditions of use in an aqueous rinsing, care, Washing and cleaning liquor are formed.

The cationically modified hydrophilic nanoparticles are, for example, by mixing of aqueous dispersions of the hydrophilic nanoparticles with an aqueous solution or dispersion of the cationic polymers, the polyvalent metal cations in the form their soluble salts or the cationic surfactants available. The cationic Component is preferably used in the form of aqueous solutions, but can one can also use aqueous dispersions of the cationic polymers, the dispersed ones Particles have an average diameter of up to 2 µm. Usually you mix them Both components at room temperature, however, can be mixed at temperatures from Z. B. 0 ° to 100 ° C, provided that the dispersions are not when heated coagulate.

The hydrophilic nanoparticles to be used according to the invention are in the water pH of the application insoluble. They are in aqueous dispersion in the form of Particles or particulate hydrogels with an average particle size of 10 nm to 2 µm, preferably 25 nm to 1 µm, particularly preferably 40 nm to 800 nm and in particular 100 to 600 nm and can be made from the aqueous dispersions as powders be won. The average particle size of the nanoparticles can e.g. B. under the Electron microscope or with the help of light scattering experiments can be determined.

The pH of the aqueous dispersions of the hydrophilic nanoparticles is in generally 1 to 6.5 and is preferably in the range of 1.5 to 5.5, particularly preferably in the range from 2 to 4.5.

The hydrophilic nanoparticles to be used according to the invention usually show pH-dependent solubility and swelling behavior. The swelling behavior depends on the monomer composition, the average molecular weight of the polymers and the temperature. Particularly at pH values below 6.5, preferably below 5.5 preferably below 4.5, the particles are water-insoluble and keep theirs particulate character or particulate hydrogel character when dispersed in concentrated as well as in dilute aqueous media. In contrast, the Hydrophilic nanoparticles used according to the invention in water under neutral,  swell strongly or partially or particularly under alkaline conditions completely dissolve.

Nanoparticles used according to the invention contain uncrosslinked polymers

• a) 60 to 100 wt .-%, preferably 70 to 99 wt .-%, particularly preferably 75 to 95% by weight of one or more carboxyl-containing ethylenically unsaturated monomers or their salts,
• b) 0 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight of one or more water-insoluble monoethylenically unsaturated monomers
• c) 0 to 25% by weight, preferably 0 to 15% by weight, particularly preferably 0.1 to 5 wt .-% one or more sulfonic acid and / or phosphonic acid groups containing monomers or their salts,
• d) 0 to 30% by weight, preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight of one or more water-soluble nonionic monomers.

Preferred carboxyl group-containing ethylenically unsaturated monomers a) are α, β-unsaturated C ₃ -C ₆ carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, itaconic acid, maleic acid, itaconic acid semiesters of C ₁ -C ₆ alcohols, maleic acid or maleic acid semiesters of C ₁ -C ₆ alcohols. Acrylic acid, methacrylic acid, maleic acid or maleic acid semiesters of C ₁ -C ₆ alcohols are particularly preferred. Methacrylic acid is particularly preferred.

Water-insoluble monomers b) are all monomers which are less than 50 g / l soluble in water at room temperature. These are monomers from the group of the alkyl esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids and monohydric C ₁ -C ₂₂ alcohols, hydroxyalkyl esters of monoethylenically unsaturated C ₃ -C ₅ carboxylic acids and divalent C ₂ -C ₄ - Alcohols, vinyl esters of saturated C ₁ -C ₁₈ carboxylic acids, ethylene, propylene, isobutylene, C ₄ -C ₂₄ alpha-olefins, butadiene, styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluoroethylene, chlorotrifluoroethylene, hexafluoropropene , Esters and amides with C ₃ -C ₅ - monoethylenically unsaturated carboxylic acids with alcohols or amines containing perfluoroalkyl groups, allyl and vinyl esters of carboxylic acids containing perfluoroalkyl groups, or mixtures thereof. Higher proportions of water-insoluble monomers b) are preferably present in the polymers when very polar monomers a) such as acrylic acid, itaconic acid and maleic acid or monomers c) or d) in a larger amount, for example in excess of 10% by weight, in particular in excess 20 wt .-% are contained in the polymer.

Preferred water-insoluble monomers b) are acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, (meth) acrylate of perfluoroalkyl-substituted alcohols CF ₃ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH or C ₂ F ₅ - (C ₂ F ₄ ) _n - (CH ₂ ) _m -OH with n = 2-8, m = 1 or 2, vinyl acetate, vinyl propionate, Styrene, ethylene, propylene, butylene, isobutene, diisobutene and tetrafluoroethylene, particularly preferred water-insoluble monomers b) are methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate and vinyl acetate.

Suitable monomers c) containing sulfonic acid or phosphonic acid groups are for example acrylamido-2-methyl-propanesulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, vinylphosphonic acid and the alkali and ammonium salts thereof Monomers.

Suitable water-soluble monomers d) have a solubility of at least 50 g / l Water at room temperature. Suitable monomers d) are, for example, acrylamide, Methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyloxa zolidone, methyl polyglycol acrylates, methyl polyglycol methacrylates and methyl polyglycol acrylamides. Monomers d) which are preferably used are vinylpyrrolidone, acrylamide and N-vinyl formamide.

Characteristic feature of the uncrosslinked polymers contained in the nanoparticles is its particular, d. H. unresolved character under the conditions of application. This particulate character is preferred at a pH below 6.5 below 5.5, particularly preferably below 4.5 for most Given compositions. In the case of high proportions of readily water-soluble monomers a), c) or d) it may be necessary to lower the pH further during use, e.g. B. under 3 or under 2 to ensure the particulate character. In the case of very small Particles in the range of 10-100 nm can only do so under certain circumstances  using special techniques such as electron microscopy.

Uncrosslinked polymers from the monomers a) and optionally b), c) and / or d) can by the known methods of solution, precipitation, suspension or Emulsion polymerization of the monomers using free radicals Polymerization initiators are produced. Preferably the hydrophilic Nanoparticles obtained by the process of emulsion polymerization in water. The Polymers have, for example, molecular weights from 1000 to 5,000,000, preferably from 5000 to 1,000,000, mostly the molecular weights of the polymers are in the range of 10,000 to 500,000.

In addition to the polymerization processes mentioned, other processes are also available Production of the hydrophilic nanoparticles into consideration. So you can z. B. polymers through Precipitation lowering the solubility of the polymers in the solvent. Such The method is, for example, that a polymer containing acid groups dissolves in a suitable water-miscible solvent and thus in an excess Water doses that the pH value of the template is at least 1 lower than that Equivalence pH of the polymer. Under equivalence pH the pH is too understand, in which 50% of the acidic groups of the polymer are neutralized. With this Processes may require a dispersing aid, pH regulators and / or Add salts to obtain stable, finely divided dispersions.

The aqueous dispersions of the hydrophilic nanoparticles can be mixed with anionic, nonionic or betaine emulsifiers and / or protective colloids can be stabilized. The emulsifiers and protective colloids can already be used as dispersants in the Production of the nanoparticles may be included or added subsequently.

Examples of anionic emulsifiers are anionic surfactants and soaps. Alkyl and alkenyl sulfates, sulfonates, phosphates and phosphonates, alkyl and alkenylbenzenesulfonates, alkyl ether sulfates and phosphates, saturated and unsaturated C ₁₀ -C ₂₅ -carboxylic acids and their salts can be used as anionic surfactants.

Nonionic and / or betaine emulsifiers can also be used. A Description of suitable emulsifiers can be found e.g. B. in Houben Weyl, Methods of  organic chemistry, volume XIV / 1, macromolecular substances, Georg Thieme Verlag, Stutt gart, 1961, pages 192 to 208.

Examples of anionic protective colloids are water-soluble anionic polymers. there very different types of polymers can be used. Preferably come anionically substituted polysaccharides and / or water-soluble anionic copolymers of acrylic acid, methacrylic acid, maleic acid, maleic acid semi-esters, vinyl sulfonic acid, Styrenesulfonic acid or acrylamidopropanesulfonic acid with other vinylic Monomers used. Suitable anionically substituted polysaccharides are e.g. B. Carboxymethyl cellulose, carboxymethyl starch, oxidized starch, oxidized cellulose and other oxidized polysaccharides and the corresponding derivatives of the freely degraded Polysaccharides. Suitable water-soluble anionic copolymers are, for example Copolymers of acrylic acid with vinyl acetate, acrylic acid with ethylene, acrylic acid with Acrylamide, acrylamidopropanesulfonic acid with acrylamide or acrylic acid with styrene.

Non-ionic and / or betaine protective colloids can also be used. A An overview of commonly used protective colloids can be found in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 411 to 420.

Polymers can be used for the production of dispersions of hydrophilic nanoparticles only contain monomers a) and optionally b) in water at a pH below 6.5 disperse. It is often advantageous to use nonionic emulsifiers or Use protective colloids. Polymers containing at least one are preferably used Monomer c) contain in copolymerized form and / or emulsify the polymers with at least an anionic emulsifier and / or stabilizes the dispersion with at least one anionic protective colloid.

To stabilize hydrophilic nanoparticles to be used according to the invention contain anionic groups, additional dispersions can be added Add polymers. Such polymers are, for example, polysaccharides, Polyvinyl alcohols and polyacrylamides.

Hydrophilic nanoparticle polymers can also be produced by: a melt of the hydrophilic polymers is emulsified in a controlled manner. For this, z. B. that Molten polymer or a mixture of the polymer with further additives and  under the influence of strong shear forces, e.g. B. in an Ultra-Turrax, so in excess Water doses that the pH of the template is at least 1 lower than that Equivalence pH of the polymer. It may be necessary to Add emulsifying agents, pH regulators and / or salts to create stable fine particles To obtain dispersions. In this variant, too, the production of finely divided polymer Additional polymers such as polysaccharides, polyvinyl alcohols or Use polyacrylamides, especially if the hydrophilic polymer contains anionic groups.

Another method of producing hydrophilic nanoparticles, the anionic groups contain, consists in that aqueous, alkaline solutions of the polymers preferably mixed with an acid under the action of strong shear forces.

The cationically modified, hydrophilic to be used according to the invention Nanoparticles can be obtained by covering the surface of the hydrophilic nanoparticles with cationic polymers, polyvalent metal ions and / or cationic surfactants.

In the treatment of anionically adjusted dispersions of the hydrophilic Nanoparticles with an aqueous solution of a cationic polymer become the Originally anionically dispersed particles reloaded so that after treatment preferably carry a cationic charge. For example, have cationic modified dispersions of particulate hydrophilic nanoparticles in 0.1 wt. % aqueous dispersion at pH 4 an interface potential of -5 to +50 mV, preferably from -2 to +25 mV, in particular from 0 to +15 mV. The interfaces potential is determined by measuring the electrophoretic mobility in dilute aqueous dispersion at the pH of the intended application liquor.

All natural or synthetic cationic polymers can be used as cationic polymers Polymers are used which contain amino and / or ammonium groups and are water soluble. Examples of such cationic polymers are vinylamine units containing polymers, vinylimidazole units containing polymers, quaternary Polymers containing vinylimidazole units, condensates of imidazole and Epichlorohydrin, cross-linked polyamidoamines, cross-linked grafted with ethyleneimine Polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, cross-linked Polyethyleneimines, amidated polyethyleneimines, alkylated polyethyleneimines, polyamines, Amine-epichlorohydrin polycondensates, alkoxylated polyamines, polyallylamines,  Polydimethyldiallylammoniumchloride, basic (meth) acrylamide or ester units containing polymers, basic quaternary (meth) acrylamide or ester units containing polymers, and / or lysine condensates.

Cationic polymers are also understood to mean amphoteric polymers, the one have net cationic charge, d. H. the polymers contain both anionic and also polymerized cationic monomers, but the molar fraction is the im Polymers contain cationic units larger than that of the anionic units.

Polymers containing vinylamine units are prepared, for example, from open-chain N-vinylcarboxamides of the formula (I)

from in which R ¹ and R ^{2 may be the} same or different and represent hydrogen and C ₁ - to C ₆ -alkyl. Suitable monomers are, for example, N-vinylformamide (R ¹ = R ² = H in formula I) N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethylacetamide, N- Vinyl-N-methylpropionamide and N-vinyl propionamide. To prepare the polymers, the monomers mentioned can be polymerized either alone, as a mixture with one another or together with other monoethylenically unsaturated monomers. Homopolymers or copolymers of N-vinylformamide are preferably used. Polymers containing vinylamine units are known, for example, from US Pat. No. 4,421,602, EP-A-0 216 387 and EP-A-0 251 182. They are obtained by hydrolysis of polymers which contain the monomers of the formula I in copolymerized form with acids, bases or enzymes.

Suitable monoethylenically unsaturated monomers which are copolymerized with the N-vinylcarboxamides are all compounds which can be copolymerized therewith. Examples include vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl ethers such as C ₁ - to C ₆ -alkyl vinyl ether, e.g. B. methyl or ethyl vinyl ether. Further suitable comonomers are ethylenically unsaturated C ₃ - to C ₆ -carboxylic acids, for example acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid and vinyl ester acid as well as their alkali metal and alkaline earth metal salts, esters, amides and nitriles of the carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate and ethyl acrylate ethyl methacrylate.

Other suitable monoethylenically unsaturated monomers which are associated with the N- Copolymerized vinyl carboxamides are carboxylic acid esters that differ from Derive glycols or polyalkylene glycols, with only one OH group being esterified is, e.g. B. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, Hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and Acrylic acid monoesters of polyalkylene glycols with a molecular weight of 500 to 10,000. Other suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, Dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basic acrylates can be in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or the Sulfonic acids or used in quaternized form. suitable Quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, Ethyl chloride or benzyl chloride.

Other suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as Acrylamide, methacrylamide and N-alkyl mono- and diamide from monoethylenic unsaturated carboxylic acids with alkyl radicals of 1 to 6 carbon atoms, e.g. B. N-methyl acrylamide, N, N-dimethylacrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-propylacrylamide and tert. Butylacrylamide and basic (Meth) acrylamides, e.g. B. dimethylaminoethyl acrylamide, Dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, Diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, Diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and Diethylaminopropylmethacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, Acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as z. B. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5- methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinyl  imidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. N-vinyl imidazole and N-vinylimidazolines are used in addition to the free bases Mineral acids or organic acids neutralized or in quaternized form used, the quaternization preferably using dimethyl sulfate, diethyl sulfate, Methyl chloride or benzyl chloride is made. Also come into question Diallyldialkylammoniumhalide such as. B. Diallyldimethylammonium Chloride.

In addition, monomers containing sulfo groups such as for example vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfone acid, the alkali metal or ammonium salts of these acids or acrylic acid-3-sulfo propyl ester in question, the content of the amphoteric copolymers being cationic Units exceeds the content of anionic units, making the polymers total have a cationic charge.

The copolymers contain, for example

• - 99, 99 to 1 mol%, preferably 99.9 to 5 mol% of N-vinylcarboxamides Formula I and
• - 0.01 to 99 mol%, preferably 0.1 to 95 mol% of other copolymers therewith sizable monoethylenically unsaturated monomers

in polymerized form.

In order to prepare polymers containing vinylamine units, one preferably starts from homopolymers of N-vinylformamide or from copolymers which are obtained by copolymerizing

• - N-vinylformamide with
• - Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinyl caprolactam, N-vinyl urea, acrylic acid, N-vinyl pyrrolidone or C ₁ - to C ₆ -alkyl vinyl ethers

and subsequent hydrolysis of the homopolymers or copolymers to form Vinylamine units are available from the copolymerized N-vinylformamide units, where the degree of hydrolysis z. B. is 0.1 to 100 mol%.  

The polymers described above are hydrolysed by known processes by the action of acids, bases or enzymes. In this way, the copolymerized monomers of the formula (I) given above are formed by splitting off the grouping

where R ^{2 has} the meaning given for it in formula I, polymers, the vinylamine units of the formula (III)

contain in which R ^{1 has} the meaning given in formula I. If acids are used as the hydrolysis agent, the units (III) are present as the ammonium salt.

The homopolymers of N-vinylcarboxamides of the formula (I) and their Copolymers can be hydrolyzed to 0.1 to 100, preferably 70 to 100 mol%. In most cases, the degree of hydrolysis of the homo- and copolymers is 5 to 95 mol%. The degree of hydrolysis of the homopolymers is synonymous with the content the polymers on vinylamine units. For copolymers, the vinyl esters contain in copolymerized form, in addition to the hydrolysis of the N-vinylformamide units Hydrolysis of the ester groups occur to form vinyl alcohol units. This is especially the case when the hydrolysis of the copolymers in the presence carried out by sodium hydroxide solution. Polymerized acrylonitrile is also used in the Hydrolysis chemically changed. Here, for example, amide groups or Carboxyl groups. The homo- and copolymers containing vinylamine units can optionally contain up to 20 mol% of amidine units which, for. B. by reaction of formic acid with two adjacent amino groups or by intramolecular Reaction of an amino group with an adjacent amide group e.g. B. from polymerized N-vinylformamide is formed. The molecular weights of the vinylamine units  containing polymers are, for. B. 1000 to 10 million, preferably 10,000 to 5 million (determined by light scattering). This molar mass range corresponds for example K values from 5 to 300, preferably 10 to 250 (determined according to H. Fikentscher in 5% by weight aqueous saline solution at 25 ° C and one Polymer concentration of 0.5 wt .-%).

The polymers containing vinylamine units are preferably in salt-free form used. Salt-free aqueous solutions of vinylamine units containing Polymers can, for example, from the salt-containing described above Polymer solutions with the help of ultrafiltration on suitable membranes Separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons can be produced. Also the aqueous solutions of Other polymers containing amino and / or ammonium groups can be used an ultrafiltration in salt-free form.

Polyethyleneimines are also suitable as cationic polymers. Polyethyleneimines are produced, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids. Polyethyleneimines have, for example, molecular weights of up to 2 million, preferably from 200 to 500,000. Polyethyleneimines with molecular weights of 500 to 100,000 are particularly preferably used. Also suitable are water-soluble crosslinked polyethyleneimines which can be obtained by reacting polyethyleneimines with crosslinking agents such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units. Amidic polyethyleneimines which are obtainable, for example, by amidating polyethyleneimines with C ₁ -C ₂₂ -monocarboxylic acids are also suitable. Other suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation z. B. per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide units.

Suitable polymers containing amino and / or ammonium groups are also Polyamidoamines, for example by condensing dicarboxylic acids with Polyamines are available. Suitable polyamidoamines are obtained, for example, by that dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines converts that contain 3 to 10 basic nitrogen atoms in the molecule. suitable Dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid,  Glutaric acid, suberic acid, sebacic acid or terephthalic acid. When producing the Polyamidoamines can also use mixtures of dicarboxylic acids, as well Mixtures of several polyalkylene polyamines. Suitable polyalkylene polyamines are for example diethylene triamine, triethylene tetramine, tetraethylene pentamine, Dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylene diamine and bis-aminopropylethylene diamine. The dicarboxylic acids and polyalkylene polyamines are heated to higher temperatures to produce the polyamidoamines, z. B. to temperatures in the range of 120 to 220, preferably 130 to 180 ° C. The Water generated during the condensation is removed from the system. In the Condensation can optionally also include lactones or lactams of carboxylic acids Use 4 to 8 carbon atoms. One uses, for example, per mole of a dicarboxylic acid 0.8 to 1.4 moles of a polyalkylene polyamine.

Other polymers containing amino groups are grafted with ethyleneimine Polyamidoamines. They are made from the polyamidoamines described above Reaction with ethyleneimine in the presence of acids or Lewis acids such as Sulfuric acid or boron trifluoride etherates at temperatures of, for example, 80 to 100 ° C available. Compounds of this type are described, for example, in DE-B-24 34 816 described.

The optionally crosslinked polyamidoamines, if appropriate, additionally before grafting with ethyleneimine come in as cationic polymers Consideration. The crosslinked polyamidoamines grafted with ethyleneimine are water-soluble and have z. B. an average molecular weight of 3000 to 1 million daltons. Usual crosslinkers are z. B. epichlorohydrin or bischlorohydrin ether of alkylene glycols and Polyalkylene glycols.

Further examples of cationic polymers, the amino and / or ammonium groups contain are polydiallyldimethylammonium chlorides. These are polymers also known.

Other suitable cationic polymers are copolymers of, for example, 1 to 99 mol%, preferably 30 to 70 mol% of acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% of cationic monomers such as Dialkylaminoalkyl acrylamide, ester and / or methacrylamide and / or methacrylic ester.  

The basic acrylamides and methacrylamides are also preferably in a form neutralized with acids or in quaternized form. Examples are given
N-Trimethylammoniumethylacrylamidchlorid,
N-Trimethylammoniumethylmethacrylamidchlorid,
N-Trimethylammoniumethylmethacrylesterchlorid,
N-Trimethylammoniumethylacrylesterchlorid,
Trimethylammoniumethylacrylamidmethosulfat,
Trimethylammoniumethylmethacrylamidmethosulfat,
N-Ethyldimethylammoniumethylacrylamidethosulfat,
N-Ethyldimethylammoniumethylmethacrylamidethosulfat,
Trimethylammoniumpropylacrylamidchlorid,
trimethylammoniumpropylmethacrylamide chloride,
Trimethylammoniumpropylacrylamidmethosulfat,
Trimethylammonium propyl methacrylamide methosulfate and
N-Ethyldimethylammoniumpropylacrylamidethosulfat.
Trimethylammonium propyl methacrylamide chloride is preferred.

Other suitable cationic monomers for the production of (meth) acrylamide Polymers are diallyldimethylammonium halides and basic (meth) acrylates. Are suitable for. B. Copolymers of 1 to 99 mol%, preferably 30 to 70 mol% Acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol% Dialkylaminoalkyl acrylates and / or methacrylates such as copolymers of acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and Dimethylaminopropyl. Basic acrylates or methacrylates are preferably in neutralized with acids or in quaternized form. The quaternization can for example with methyl chloride or with dimethyl sulfate.

Cationic polymers which have amino and / or ammonium groups come polyallylamines are also considered. Polymers of this type are obtained from Homopolymerization of allylamine, preferably in neutralized with acids or in quaternized form or by copolymerizing allylamine with others monoethylenically unsaturated monomers as comonomers for N- Vinyl carboxamides are described.

The cationic polymers have, for. B. K values from 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% by weight aqueous saline solution at 25%  and a polymer concentration of 0.5% by weight). At pH 4.5 they have for example a charge density of at least 1, preferably at least 4 meq / g Polyelectrolyte.

Examples of preferred cationic polymers are polydimethyldiallylammonium chloride, polyethyleneimine, polymers containing vinylamine units, copolymers of acrylamide or methacrylamide containing copolymerized basic monomers, polymers containing lysine units or mixtures thereof. Examples of cationic polymers are:

• - Copolymers of 50% vinyl pyrrolidone and 50% trimethylammonium ethyl methacrylate methosulfate, M _W 1000 to 500 000;
• - Copolymers of 30% acrylamide and 70% trimethylammonium ethyl methacrylate methosulfate, M _W 1000 to 1 000 000;
• - Copolymers of 70% acrylamide and 30% dimethylaminoethyl methacrylamide, M _W 1000 to 1 000 000;
• - Copolymers of 50% hydroxyethyl methacrylate and 50% 2-dimethylaminoethyl methacrylamide, M _W 1000 to 500 000;
• - Copolymer of 70% hydroxyethyl methacrylate and 50% 2-dimethylamino ethyl methacrylamide; 30% vinylimidazole methochloride copolymer, 50% Dimethylaminoethyl acrylate, 15% acrylamide, 5% acrylic acid;
• - Polylysines with M _W from 250 to 250,000, preferably 500 to 100,000 and lysine cocondensates with molecular weights M _W from 250 to 250,000, with z. B. amines, polyamines, ketene dimers, lactams, alcohols, alkoxylated amines, alkoxylated alcohols and / or non-proteinogenic amino acids,
• - vinylamine homopolymers, 1 to 99% hydrolyzed polyvinylformamides, Copolymers of vinyl formamide and vinyl acetate, vinyl alcohol, vinyl pyrrolidone or acrylamide with molecular weights of 3000-500 000,  
• Vinylimidazole homopolymers, vinylimidazole copolymers with vinylpyrrolidone, Vinylformamide, acrylamide or vinyl acetate with molecular weights from 5000 to 500,000 as well as their quaternary derivatives,
• - Polyethyleneimines, crosslinked polyethyleneimines or amidated polyethyleneimines with Molar masses from 500 to 3,000,000,
• Amine-epichlorohydrin polycondensates which contain imidazole, piperazine, C ₁ -C ₈ -alkylamines, C ₁ -C ₈ -dialkylamines and / or dimethylaminopropylamine as amine component and which have a molecular weight of 500 to 250,000,
• - Basic (meth) acrylamide or ester unit-containing polymers, basic polymers containing quaternary (meth) acrylamide or ester units Molar masses from 10,000 to 2,000,000.

Furthermore, it is also possible to a minor extent (<10% by weight) of anionic Polymerize comonomers, e.g. As acrylic acid, methacrylic acid, vinyl sulfonic acid or alkali salts of the acids mentioned.

In order to cationically modify hydrophilic nanoparticles, they can also be modified with treat polyvalent metal ions and / or cationic surfactants. An occupancy of the Particles with polyvalent metal ions are achieved by, for example, one aqueous dispersion of anionically dispersed hydrophilic nanoparticles an aqueous Solution or at least one water-soluble, multivalent metal salt dissolves water-soluble, polyvalent metal salt therein, whereby a modification of the anionically dispersed hydrophilic nanoparticles with cationic polymers either before, at the same time or after this treatment. Suitable metal salts are, for example, the water-soluble salts of Ca, Mg, Ba, Al, Zn, Fe, Cr or their Mixtures. Water-soluble heavy metal salts, which are derived, for example, from Cu, Ni, Deriving Co and Mn can be used in principle, but not in all applications he wishes. Examples of water-soluble metal salts are calcium chloride, calcium acetate, Magnesium chloride, aluminum sulfate, aluminum chloride, barium chloride, zinc chloride, Zinc sulfate, zinc acetate, iron (II) sulfate, iron (III) chloride, chromium (III) sulfate. Copper sulfate, nickel sulfate, cobalt sulfate and manganese sulfate. The are preferred water-soluble salts of Ca, Al and Zn used for the cationic modification.  

The transfer of the hydrophilic nanoparticles is also possible with cationic surfactants. Cationic surfactants with different structures are potentially suitable for this. A An overview of a selection of suitable cationic surfactants is in Ullmanns Encyclopedia Industrial Chemistry, Sixth Edition, 1999, Electronic Release, Chapter "Surfactants", Chapter 8, Cationic Surfacfcants.

Particularly suitable cationic surfactants are e.g. B. C ₇ - to C ₂₅ alkylamines, C ₇ - to C ₂₅ - N, N-dimethyl-N- (hydroxyalkyl) ammonium salts with alkylating agents quaternized mono- and di- (Cr- to C ₂₅ -) - alkyldimethylammonium compounds, esterquats such as quaternary esterified mono-, di- or trialkanolamines esterified with C ₈ -C ₂₂ -carboxylic acids, imidazoline quats such as 1-alkyllimidazolinium salts of the general formulas

wherein
R ¹ = C ₁ -C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl,
R ² = C ₁ -C ₄ alkyl or hydroxyalkyl and
R ³ = C ₁ -C ₄ alkyl, hydroxyalkyl or an R ₁ - (C = O) -X- (CHZ) - with X = O or NH and
n = 2 or 3
mean and wherein at least one radical R ¹ = C ₇ -C ₂₂ alkyl.

For many commercial and technical applications and everyday applications is the dirt-removing modification of textiles, textile surfaces, Leather, wood, smooth and textured hard surfaces matter. For example come as surfaces of textile and non-textile to be treated according to the invention Materials microscopic hard surfaces, floor and wall coverings, glass surfaces, Ceramic surfaces, stone surfaces, concrete surfaces, metal surfaces, enamelled Surfaces, plastic surfaces, wooden surfaces, surfaces of coated  Wooden or lacquered surfaces are considered. Coming as microscopic surfaces z. B. porous bodies such as foams, woods, leather, porous building materials, porous minerals in Consideration. Other suitable surfaces are floor or wall paintings or coatings and cellulose nonwovens. It is not always possible to modify the Surfaces through soaking and painting processes with concentrated formulations perform. Often it is desirable to modify with the help of a rinse of the material to be treated with a highly diluted, the active substance containing liquor to carry out or the modification by spraying a strong to achieve dilute aqueous formulation. It is often an advantage Modification of the surfaces of the materials to be treated with a wash, Combine cleaning and / or care or impregnation of the surface.

All types of fiber fabrics, covers and coverings come in as textile materials Consider, both synthetic fibers and natural fibers and modified natural fibers can be treated. In particular, textiles come from cotton fabrics, modified cotton such as B. viscose, cotton blended fabrics such. B. Tree wool / polyester blend and cotton polyamide blend and textiles made of finished fabrics or fibers. Other types of preferentially treated textile surfaces are e.g. B. carpets, upholstery and decorative fabrics.

Further surfaces to be treated preferably with nanoparticles according to the invention are all types of smooth and rough leather. Of particular interest is the Modification of rough leather surfaces (e.g. from Suede) of leather clothing, shoes and furniture.

Further surfaces to be treated preferably with nanoparticles according to the invention are plastic floor coverings such as B. linoleum or PVC.

The modification of the surfaces of the above materials mainly consists of a dirt-removing effect by treatment with the Cationically modified hydrophilic nanoparticles according to the invention. That is one Facilitation of dirt removal during subsequent washing, rinsing or Cleaning. In addition, other effects such. B. a reduction in Dirt liability, protection against chemical or mechanical influences or Damage, an improvement in the structure retention of fibers, an improvement in the Preservation of shape and structure of fabrics, a reduction of the static charge  as well as a grip improvement occur.

The concentration of the hydrophilic nanoparticles when used in the dishwashing or Care bath, in the detergent liquor or in the cleaning bath is generally 0.0002 up to 1.0% by weight, preferably 0.0005 to 0.25% by weight, particularly preferably 0.002 to 0.05% by weight.

The respective surfaces are treated with cationic agents according to the invention modified hydrophilic nanoparticles from aqueous liquors or rinsing or Spray formulations, for example 2.5 to 300 ppm, preferably 5 to 200 ppm and in particular 10 to 100 ppm of one or more cationic polymers and / or 1 up to 6 mmol / l, preferably 1.5 to 4 mmol / l one or more water-soluble salts of divalent metals, especially salts of Ca, Mg or Zn and / or 0.05 to 2 mmol / l, preferably 0.1 to 0.75 mmol / l one or more water-soluble Al salts and / or contain 1 to 600 ppm, preferably 10 to 300 ppm, of cationic surfactants.

If cationically modified nanoparticles according to the invention are used as additives, can on the addition of other cationic polymers, polyvalent metal ions or cationic surfactants are completely or partially dispensed with.

The rinsing liquor or the formulation to be sprayed on is generally prepared by diluting concentrated formulations with water or predominantly aqueous solvents. If this dilution is carried out with water which contains at least 1.0 mmol of Ca ²⁺ and / or Mg ²⁺ , preferably at least 1.5 mmol / l, particularly preferably at least 2.0 mmol / l, treatment with dispersions of the hydrophilic nanoparticles can be carried out also without the addition of cationic polymers, polyvalent metal ions and / or cationic surfactants.

Agents according to the invention for the treatment of surfaces in dilution with water solid, the liquid can be used. Solid agents can be powdered, Granules or tablets are present and are dissolved in water for use or dispersed, the nanoparticles of the invention dispersed after dilution distributed.

The cationic modification of the hydrophilic nanoparticles is preferably carried out before Use in aqueous treatment agents. However, it can also be used in manufacturing  the aqueous treatment agent or when using non-cationic modified hydrophilic nanoparticles are made by z. B. aqueous dispersions the hydrophilic nanoparticles with the other components of each Treatment agent in the presence of cationic polymers, water-soluble salts mixes multivalent metals and / or cationic surfactants.

In a special embodiment, the non-cationically modified ones can also be used Nanoparticles or formulations containing these particles directly in the dishwashing, washing or Add cleaning liquor if it is ensured that sufficient amounts are in the liquor on cationic polymers and / or polyvalent metal ions and / or cationic Dissolved surfactants. For example, it is possible that it is not cationic modified hydrophilic nanoparticles or formulations containing these particles in Fleets with a cationic polymer content of 2.5 to 300 ppm water-soluble salts of Ca, Mg or Zn of over 0.5 mmol / l, preferably over 1.0 mmol / l, particularly preferably over 2.0 mmol / l. If cationic surfactants are used, they are used for example in concentrations of 50 to 1000 ppm, preferably 75 to 500 ppm and in particular from 100 to 300 ppm in the aqueous fleet.

The hydrophilic, non-cationically modified nanoparticles or these nanoparticles Formulations containing can also before, after or at the same time with a cationic Polymers containing polyvalent metal ions and / or cationic surfactants Formulation of the rinse liquor are added.

The present invention also relates to an agent for treating surfaces of textile or non-textile materials that promote the removal of dirt, comprising:

• a) 0.05 to 40% by weight of hydrophilic nanoparticles,
• b) 0 to 30% by weight of one or more cationic polymers, cationic surfactants and / or water-soluble salts of Mg, Ca, Zn or Al,
• c) 0 to 20% by weight of acid,
• d) 0 to 80% by weight of conventional additives such as bases, inorganic builders, organic Cobuilder, other surfactants, polymeric color transfer inhibitors, polymeric  Graying inhibitors, further soil release polymers other than (a), Enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, Light stabilizers, dyes, non-aqueous solvents, adjusting agents, hydrotropes, Thickeners and / or alkanolamines.
• e) 0 to 99.95 wt .-% water.

In one embodiment, the agents according to the invention contain 0.01 to 10% by weight Acid. In a further embodiment, the agents according to the invention contain 0.01 to 40% by weight of conventional additives. In a further embodiment, the agents according to the invention 50 to 95 wt .-% water.

Agents according to the invention for the treatment of surfaces which are used in dilution with water can, for example, have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles
• b) 0 to 20% by weight of acid
• c) 0.01 to 80% by weight of conventional additives such as acids, bases, inorganic builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric Graying inhibitors, further soil release polymers other than (a), Enzymes, perfume substances, complexing agents, corrosion inhibitors, waxes, Silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, Thickeners and / or alkanolamines.

Preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles
• b) 0.1 to 30% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,
• c) 0 to 20% by weight of acid,  
• d) 0 to 80% by weight of conventional additives such as bases, inorganic builders, organic Cobuilders, surfactants, polymeric color transfer inhibitors, polymeric Graying inhibitors, further soil release polymers other than (a), Enzymes, perfume substances, complexing agents, corrosion inhibitors, waxes, Silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, Thickeners and / or alkanolamines.

Further preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles,
• b) 0.1 to 10% by weight of acid,
• c) 0 to 80 wt .-% of at least one conventional additive such as bases, inorganic Builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, other soil release agents other than (a) Polymers, enzymes, perfumes, complexing agents, corrosion inhibitors, waxes, Silicone oils, light stabilizers, dyes, non-aqueous solvents, hydrotropes, Thickeners and / or alkanolamines.

Particularly preferred agents according to the invention for the treatment of surfaces which are used in dilution with water have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles,
• b) 0.01 to 30 wt .-% cationic polymers, water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants
• c) 0.1 to 10% by weight of acid,
• d) 0.01 to 80% by weight of at least one customary additive, such as bases, inorganic builders, organic cobuilders, other surfactants, polymers Color transfer inhibitors, polymeric graying inhibitors, others, from (a) various soil release polymers, enzymes, perfumes, complexing agents,  Corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, not aqueous solvents, hydrotropes, thickeners and / or alkanolamines.

Liquid agents are present as a dispersion, the dispersion also being complete can be transparent if very small nanoparticles according to the invention are used or whose concentration is very low. Liquid agents according to the invention have one pH below 6.5, preferably below 5.5, particularly preferably below 4.5.

Liquid detergents for treating surfaces that are used in dilution with water can also have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles,
• b) 0.1 to 10% by weight of acid,
• c) 0.01 to 40% by weight of at least one customary additive, such as bases, inorganic builders, organic cobuilders, surfactants, polymers Color transfer inhibitors, polymeric graying inhibitors, others, from (a) various soil release polymers, enzymes, perfumes, complexing agents, Corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, not aqueous solvents, hydrotropes, thickeners and / or alkanolamines.
• d) 50-95% by weight water

the pH of the agent is from 1 to 6.5.

Preferred liquid agents for the anti-soiling treatment of surfaces which are used in dilution with water can also have the following composition:

• a) 0.1 to 40% by weight of hydrophilic nanoparticles,
• b) 0.01 to 30 wt .-% cationic polymers, water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,  
• c) 0.1 to 10% by weight of acid,
• d) 0.01 to 40% by weight of at least one customary additive, such as bases, inorganic builders, organic cobuilders, surfactants, polymers Color transfer inhibitors, polymeric graying inhibitors, others, from (a) various soil release polymers, enzymes, perfumes, complexing agents, Corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, Solvents, hydrotropes, thickeners and / or alkanolamines,
• e) 50-95 wt .-% water

the pH of the agent is from 1 to 6.5.

In the formulations described above, component (b) can be composed, for example, as follows:

• 1. 0.01 to 10 wt .-% cationic polymers and / or
• 2. 0.01 to 30% by weight of water-soluble salts of Mg, Ca, Zn or Al and / or
• 3. 0.01 to 30% by weight of cationic surfactants,

each based on the total weight of the agent, the sum of (b1) to (b3) is a maximum of 30% by weight.

Suitable acids (c) are both mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid or organic acids such as carboxylic acids or sulfonic acids, strong mineral acids and sulfonic acids being used either diluted in a small amount below 5% by weight or as partially neutralized acid salts. C ₁ -C ₃ monocarboxylic acids, C ₂ -C ₁₈ dicarboxylic acids and C ₆ -C ₁₈ tricarboxylic acids are preferably used. In particular, C ₃ -C ₁₄ alkenyl succinic acids, maleic acid, adipic acid, malic acid, tartaric acid, butanetetracarboxylic acid and citric acid are formic acid, acetic acid, lactic acid, oxalic acid, succinic acid, C ₃ -C ₁₄ -Alkylbernsteinsäure used.

Detergent-promoting laundry treatment and laundry care products contain, for example

• a) 0.1 to 30% by weight of hydrophilic nanoparticles,
• b) 0.1 to 10% by weight of cationic polymers, water-soluble salts of Mg, Ca, Zn or Al and / or cationic surfactants,
• c) 0.05 to 20% by weight of a carboxylic acid such as formic acid, citric acid, Adipic acid, succinic acid, oxalic acid or mixtures thereof,
• d) 0 to 10% by weight of other customary ingredients, such as perfume, silicone oil, Light stabilizers, dyes, complexing agents, graying inhibitors, others, of (a) different soil release polymers, color transfer inhibitors, not aqueous solvents, hydrotropes, thickeners and / or alkanolamines and
• e) 30 to 99.65 wt .-% water.

Preferred laundry detergent and laundry detergent to promote soil release

• a) 1 to 30% by weight of hydrophilic nanoparticles,
• b) 0.1 to 30% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn and / or Al and / or cationic surfactants,
• c) 1 to 15% by weight of a carboxylic acid such as formic acid, citric acid, adipic acid, Succinic acid, oxalic acid or mixtures thereof,
• d) 0 to 10% by weight of at least one other customary ingredient, such as perfume, Silicone oil, light stabilizers, dyes, complexing agents, graying inhibitors, Soil-release polyester, color transfer inhibitors, non-aqueous solvents, Hydrotropes, thickeners and / or alkanolamines and
• e) 15 to 97.9% by weight of water.

Component (b) can, for example, consist of

• 1. 0.1 to 10% by weight of cationic polymers and / or
• 2. 0.1 to 30% by weight of water-soluble salts of Mg, Ca, Zn and / or Al, the Content of water-soluble salts of aluminum
• 3. 0.1 to 30% by weight of cationic surfactants,

in each case based on the total weight of the laundry treatment or Laundry detergent, the sum of components (b1) to (b3) 0.1 to 30% by weight results, exist.

Component (b2) can consist, for example, of 0.1 to 30% by weight of water-soluble salts of Mg, Ca and / or Zn and / or 0.1 to 10% by weight of water-soluble salts of Aluminum exist, based on the total weight of the laundry treatment or Laundry care agent.

Another application of the cationically modified hydrophilic nanoparticles according to the invention consists in spraying dilute aqueous formulations onto the surface to be treated. This can be done in the home or in commercial use by spraying using a spray bottle or an automatic spraying device. The formulations suitable for this have, for example, the following compositions:

• a) 0.005 to 2% by weight of hydrophilic nanoparticles,
• b) 0.0005 to 1% by weight of cationic polymers and / or water-soluble salts of Mg, Ca, Zn and / or Al and / or cationic surfactants,
• c) 0 to 10 wt .-% of at least one conventional additive such as bases, inorganic Builders, organic cobuilders, surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers different from (a), Enzymes, perfume substances, complexing agents, corrosion inhibitors, waxes, Silicone oils, light stabilizers, dyes, solvents, hydrotropes, thickeners and / or alkanolamines.
• d) 87-99.9945% by weight of water,

the pH of the agent is from 1 to 6.5.

The usual additives used in formulations according to the invention are for example in "Ullmanns Enzyclopedia of Industrial Chemistry, Sixth Edition, 2000, Electronic Version 2.0 "described in detergents, cleaning agents and Additives used in textile rinse agents.

The following are particularly suitable as surfactants and cobuilders:
Anionic surfactants, especially:

• - (Fat) alcohol sulfates of (fatty) alcohols with 8 to 22, preferably 10 to 18 carbon atoms, e.g. B. C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₄ alcohol sulfates, C _{12 to} C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
• - sulfated alkoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates). Compounds of this type are prepared, for example, by firstly using a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation;
• linear C ₈ to C ₂₀ alkyl benzosulfonates (LAS), preferably linear C ₉ to C ₁₈ alkyl benzene sulfonates and alkyl toluenesulfonates,
• - Alkane sulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ alkane sulfonates
• - Soaps such as the Na and K salts of C ₈ to C ₂₄ carboxylic acids.

The anionic surfactants mentioned are preferably in the form of Added salts. Suitable cations in these salts are alkali metal ions such as Sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium.  

Nonionic surfactants, especially:

• - Alkoxylated C ₈ - to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of one of the above-mentioned alkylene oxides added can be used as surfactants. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. The nonionic surfactants generally contain 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide per mole of alcohol. These preferably contain ethylene oxide as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;
• Alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units;
• - Alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain and generally 1 to 20, preferably 1.1 to 5 glucoside units;
• - N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and Block copolymers of ethylene oxide, propylene oxide and / or butylene oxide.

Suitable inorganic builders are in particular:

• - Crystalline or amorphous aluminosilicates with ion exchange properties such as especially zeolites. Suitable zeolites are in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially against others Cations such as Li, K, Ca, Mg, or ammonium are exchanged;
• - Crystalline silicates such as, in particular, disilicate or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates;
• Amorphous silicates such as sodium metasilicate or amorphous disilicate;  
• - carbonates and hydrogen carbonates. These can be in the form of their alkali metal, Alkaline earth metal or ammonium salts are used. Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or sodium hydrogencarbonate;
• - Polyphosphates such as B. pentasodium triphosphate;

Suitable organic cobuilders are in particular low molecular weight, oligomeric or polymeric carboxylic acids.

• Suitable low-molecular carboxylic acids are, for example, citric acid, Hydrophobically modified citric acid such as B. agaricic acid, malic acid, Tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, Oxydisuccinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetra carboxylic acid, alkyl and alkenyl succinic acids and aminopolycarboxylic acids such as z. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, Serine diacetic acid, isoserine diacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, Ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid;
• - Suitable oligomeric or polymeric carboxylic acids are, for example, homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C ₂ -C ₂₂ olefins such as. B. isobutene or long-chain α-olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, vinyl acetate, vinyl propionate, (meth) acrylic esters of C ₁ -C ₈ alcohols and styrene. The homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid are preferably used.

Polyaspartic acids are also suitable as organic cobuilders. The oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt.

The invention is illustrated by the examples below.  

Examples dispersions

Examples of typical anionic dispersions obtained by mixing with cationic Polymers, water-soluble salts of polyvalent metals and / or cationic surfactants and other components can be processed into detergents, cleaning agents or care products can be, the dispersions described below 1 to 3, the dispersed Particles in dynamic light scattering as discrete particles with the specified average particle diameter can be observed.

With the nanoparticles to be used according to the invention, one achieves in particular Cotton and cellulose fibers have a much higher soil release effect than with known methods.

The particle size distribution was determined using the "Autosizer 2C" from Malvern, GB, measured. The measurement was carried out at 23 ° C. Solutions are, unless otherwise is specified, aqueous solutions. The indication pphm used in the examples means parts by weight based on 100 parts by weight of total monomers.

Dispersion 1

In a polymerization vessel equipped with a stirrer, reflux condenser, dosing devices and Equipped for working under a nitrogen atmosphere, you put 66.8 g an oxidatively degraded starch with a degree of carboxylate substitution of 0.03 to 0.04 and a K value of 34 (determined in accordance with DIN 53 726, Amylex 15 from Südstark) and 726 g of water and heated to a temperature of 85 ° C. in 25 minutes with stirring. Then 0.2 g of a 25% by weight aqueous calcium acetate solution and 10 g are added a 10.5 g of a 1% by weight commercial enzyme solution (alpha-amylase, Termamyl 120 L from Novo Nordisk). After 15 minutes the enzymatic starch breakdown stopped by adding 6 g of glacial acetic acid. 16.8 g of a 1% strength by weight are also added aqueous iron (II) sulfate solution. The temperature of the reaction mixture is at 85 ° C held. At this temperature, a mixture of 55 g is added within 90 minutes Ethyl acrylate, 77.5 g methacrylic acid and 17 g acrylic acid. Simultaneously with that The initiator feed starts from the monomer feed. 42 g become one within 105 minutes  15 wt .-% hydrogen peroxide solution added. After the whole The amount of initiator has been added is cooled to 50 ° C. Then within 15 Minutes, 0.3 g of a 70% by weight tertiary butyl hydroperoxide solution were added and 30 Minutes stirred. It is then cooled to room temperature. You get one Dispersion with a solids content of 21 wt .-%, an average Particle diameter of the dispersed particles of 254 nm and a filtration residue of 0.3 g, based on the total batch.

Dispersion 2

In one with anchor stirrer, thermometer, gas inlet tube, dropping funnel and Glass reactor provided with reflux condenser are 8 g of a 2.5 wt .-% Sodium peroxydisulfate solution as initiator feed, 4 g of a 15% by weight Sodium lauryl sulfate solution and 841 g of water are introduced and stirred in a heating bath warmed, while the air is displaced by introducing nitrogen. If the heating bath has reached the preset temperature of 75 ° C, the Nitrogen introduction is interrupted and an emulsion becomes over the course of 2 hours consisting of 15 g of a 15 wt .-% sodium lauryl sulfate solution, 266 ml of water, 72 g Ethyl acrylate, 106 g methacrylic acid and 22 g acrylic acid, added dropwise to the template. To The end of the addition is polymerized at 75 ° C. for 1 hour. Then it gets to room temperature cooled and immediately 0.5 g of a 30 wt .-% are Hydrogen peroxide solution added and a solution consisting of over 15 minutes 0.2 g of ascorbic acid, 0.2 g of iron (II) sulfate and 19.8 g of water were added. You get one Dispersion with a solids content of 15 wt .-%, a particle diameter of 100 nm, a pH of 3 and a filtration residue of 0.5 g, based on the Overall approach.

Dispersion 3

In one with anchor stirrer, thermometer, gas inlet tube, dropping funnel and Glass reactor provided with reflux condenser are 8 g of a 2.5 wt .-% Sodium peroxydisulfate solution as initiator feed, 4 g of a 15% by weight Sodium lauryl sulfate solution and 841 g of water are introduced and stirred in a heating bath warmed, while the air is displaced by introducing nitrogen. If  the heating bath has reached the preset temperature of 75 ° C, the Nitrogen introduction is interrupted and an emulsion becomes over the course of 2 hours consisting of 15 g of a 15 wt .-% sodium lauryl sulfate solution, 266 ml of water, 52 g Ethyl acrylate, 126 g of methacrylic acid and 22 g of acrylic acid were added dropwise to the template. To The end of the addition is polymerized at 75 ° C. for 1 hour. Then it gets to room temperature cooled and immediately 0.5 g of a 30 wt .-% are Hydrogen peroxide solution added and a solution consisting of over 15 minutes 0.2 g of ascorbic acid, 0.2 g of iron (II) sulfate and 19.8 g of water were added. You get one Dispersion with a solids content of 15 wt .-%, a particle diameter of 100 nm, a pH of 3 and a filtration residue of 0.6 g, based on the Overall approach.

washing tests

For testing the dirt-removing properties of rinsing formulations with nanoparticles according to the invention compared to Post-rinse formulations according to the prior art were the following washing tests carried out:

example 1

Dispersion 1 was adjusted to a concentration of pH 4 with deionized water Diluted 2000 ppm and with stirring in the same amount of a solution of 200 ppm high molecular weight polyethyleneimine with a molecular weight of 1,000,000 in deionized water from pH 4 dosed. The pH was adjusted with 0.1 N HCl.

The diluted dispersion thus obtained was used as a rinse liquor.

Comparative Example 1

Dispersion 1 was adjusted to pH 4 with deionized water, adjusted with 0.1 N HCl a concentration of 1000 ppm diluted and used as a rinse liquor.  

Comparative Example 2

The aqueous solution of a copolymer according to Example 1 of US 3,836,496 of Methacrylic acid and ethyl acrylate in a weight ratio of 66.6: 33.3 was applied to a Concentration of 1000 ppm diluted with 1 N HCl to a pH of 4 set. This solution was used as a rinse liquor.

Example 2

Dispersion 2 was diluted to a concentration of 1000 ppm with water which contained 3.0 mmol / l CaCl ₂ and was adjusted to pH 4 with 0.1 N HCl. The diluted dispersion thus obtained was used as a rinse liquor.

Comparative Example 3

A solution of a copolymer with a polymer content of 1000 ppm according to Example 1 US 3,993,830 of methacrylic acid and ethyl acrylate in a weight ratio of 66.6: 33.3 was adjusted to pH 4 in water with 0.1 N HCl, the 3.0 mmol / l calcium chloride dissolved contained, manufactured. This solution was used as a rinse liquor.

Comparative Example 4

Dispersion 2 was adjusted to pH 4 with deionized water, adjusted with 0.1 N HCl a concentration of 1000 ppm diluted and used as a rinse liquor.

Example 3

33.3 g of dispersion 3 were diluted to 50 g with 1.25 M aqueous formic acid. 1.4 g of calcium chloride was diluted to 50 g with 1.25 M aqueous formic acid. The Dispersion was mixed with the calcium chloride solution with stirring. The received Formulation contained 5.0% by weight of hydrophilic nanoparticles and 126 mmol / l calcium Ions. For the rinse liquor, 16 g of the formulation were added per liter of water 0.5 mmol / l calcium chloride used.  

Comparative Example 5

33.3 g of the dispersion from Example 3 were diluted to 100 g with 1.25 M formic acid. The formulation obtained contained 5.0% nanoparticles and no calcium ions. For the Rinsing liquor was 16 g of the formulation per liter of water with 0.5 mmol / l Calcium chloride used.

In separate experiments, two 2.5 g cotton fabrics or Polyester / cotton (50:50) blended fabric (test fabric) together with 5 g ballast weave (in equal parts cotton and cotton / polyester blend) with one granular heavy-duty household detergent (Ariel Futur) washed with tap water rinsed and rinsed with the rinse liquors from Examples 1 to 3. Connect the test fabrics were dried and soiled.

In a first test series, lipstick mass was used as soiling. The Application was carried out with a brush and a stencil on a circle of 4 cm Diameter.

In a second series of tests, used motor oil was used as soiling used. The application was done by dropping 0.3 g of the oil onto the horizontal lying tissue.

The reflectance of the soiled tissue before washing at 460 nm was determined (in% remission). The fabrics were then washed with a heavy-duty detergent (Ariel Future) with the addition of 15 g of ballast fabric (in equal parts cotton and Cotton / polyester blend) washed again. To evaluate the The remission of the soiled tissue has a dirt-removing effect measured after washing at 460 nm (in% remission) and from the remission values the difference in reflectance ΔR is determined before and after washing. The values for both Tissues from an experiment were averaged and rounded to whole numerical values.

washing conditions prewash

Washing machine: Launder-0-meter
Prewash temperature: 20 ° C
Prewash time: 15 min
Fleet ratio: 25

main wash

Washing temperature: 40 ° C
Detergent: Ariel Futur
Detergent dosage: 3.5 g / l
Washing time: 30 min
Water hardness: 3 mmol / l
Ca / Mg ratio: 3: 1
Fleet ratio: 12.5

Table 1

Attempts to wash with lipstick paste as soiling

Table 2

Attempted washing with dirty motor oil as a soiling

The comparison of Example 1 with Comparative Examples 1 and 2 shows that in one Rinsing with nanoparticles in water in the absence of hardness ions is only a good thing A dirt-removing effect occurs when a cationic polymer is present. The dissolved acrylate copolymer according to US 3,836,496 shows on the cotton / polyester Mixed fabrics have no effect at the same concentration.

The comparison of Example 2 with Comparative Examples 3 and 4 shows that in one Rinsing with nanoparticles according to the invention in water in the presence of 3 mmol / l Ca ions has a very good dirt-removing effect, while in Absence of Ca ions is not observed. With the dissolved polymer according to No. 3,993,830 does not have a satisfactory effect even in the presence of 3.0 mmol of Ca ions achieved.

The comparison of example 3 with comparative example 5 shows that at low dosage of calcium ions, as z. B. in tap water from areas with soft water occurs, only the formulation according to the invention with additional calcium ions is good Effect.

Claims (15)

1. Process for the removal of dirt from surfaces of textile and non-textile materials, in which cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

• a) 60 to 100% by weight of one or more ethylenically unsaturated monomers containing carboxyl groups or their salts,
• b) 0 to 40% by weight of one or more water-insoluble monoethylenically unsaturated monomers,
• c) 0 to 25% by weight of one or more monomers containing sulfonic acid and / or phosphonic acid groups or their salts,
• d) 0 to 30% by weight of one or more water-soluble nonionic monomers

are applied from an aqueous dispersion to the surface of the materials, the dispersion of the hydrophilic nanoparticles being stabilized with anionic, nonionic and / or betaine emulsifiers and / or protective colloids, and wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 μm and are cationically modified by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants. 2. The method according to claim 1, characterized in that the aqueous dispersion Contains 0.0002 to 1 wt .-% hydrophilic nanoparticles. 3. The method according to claim 1 or 2, characterized in that the pH of the aqueous dispersion is from 1 to 6.5.   4. The method according to any one of claims 1 to 3, characterized in that the cationic polymers are selected from the group consisting of vinylamine Unit-containing polymers, vinylimidazole units containing Polymers, polymers containing quaternary vinylimidazole units, Imidazole / epichlorohydrin condensates, cross-linked polyamidoamines, with Crosslinked polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethyleneimines, amidated Polyethyleneimines, alkylated polyethyleneimines, polyamines, Amine / epichlorohydrin polycondensates, alkoxylated polyamines, Polyallylamines, polydimethyldiallylammonium chlorides, basic Polymers containing (meth) acrylamide or (meth) acrylic ester units, basic quaternary (meth) acrylamide or (meth) acrylic ester units containing polymers and lysine condensates. 5. The method according to any one of claims 1 to 3, characterized in that the polyvalent metal cations are selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Al ³⁺ and Zn ²⁺ . 6. The method according to any one of claims 1 to 4, characterized in that the cationic surfactants are selected from the group consisting of C ₇ -C ₂₅ alkylamine, C ₇ -C ₂₅ alkylammonium, di (C ₇ -C ₂₅ ) alkylammonium, C ₇ -C ₂₅ alkyl ester quat and C ₇ -C ₂₅ alkyl imidazolinium compounds. 7. Cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

• a) 60 to 100% by weight of one or more ethylenically unsaturated monomers containing carboxyl groups or their salts,
• b) 0 to 40% by weight of one or more water-insoluble monoethylenically unsaturated monomers,
• c) 0 to 25% by weight of one or more monomers containing sulfonic acid and / or phosphonic acid groups or their salts,
• d) 0 to 30% by weight of one or more water-soluble nonionic monomers,

wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 microns and are cationically modified by covering their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants. 8. Aqueous dispersions of cationically modified hydrophilic nanoparticles based on uncrosslinked polymers

• a) 60 to 100% by weight of one or more ethylenically unsaturated monomers containing carboxyl groups or their salts,
• b) 0 to 40% by weight of one or more water-insoluble monoethylenically unsaturated monomers,
• c) 0 to 25% by weight of one or more monomers containing sulfonic acid and / or phosphonic acid groups or their salts,
• d) 0 to 30% by weight of one or more water-soluble nonionic monomers,

wherein the dispersion of the hydrophilic nanoparticles can be stabilized with anionic, nonionic and / or betaine emulsifiers and / or protective colloids, and wherein the hydrophilic nanoparticles have a particle size of 10 nm to 2 μm and by coating their surface with one or more cationic polymers, one or more polyvalent metal ions and / or one or more cationic surfactants are cationically modified. 9. Aqueous dispersions according to claim 8, characterized in that they have 0.001 contain up to 50% by weight of hydrophilic nanoparticles. 10. Use of hydrophilic nanoparticles or of cationically modified hydrophilic nanoparticles as defined in claim 6 as dirt detachable additive to dishwashing, care, washing and cleaning agents.   11. Use of aqueous dispersions as defined in claim 8 or 9 are, as a dirt-removing additive to dishwashing, care, washing and Detergents. 12. Containing agents for the detachment-promoting treatment of surfaces of textile or non-textile materials

• a) 0.05 to 40% by weight of hydrophilic nanoparticles according to claim 7,
• b) 0 to 30% by weight of one or more cationic polymers, cationic surfactants and / or water-soluble salts of Mg, Ca, Zn or Al,
• c) 0 to 20% by weight of acid,
• d) 0 to 80% by weight of conventional additives such as bases, inorganic builders, organic cobuilders, further surfactants, polymeric color transfer inhibitors, polymeric graying inhibitors, soil release polymers, enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light stabilizers, dyes, solvents , Adjusting agents, hydrotropes, thickeners and / or alkanolamines.
• e) 0 to 99.95 wt .-% water.

13. Containing means according to claim 12

• a) 0.1 to 30 wt .-% cationic polymers, cationic surfactants and / or water-soluble salts of Mg, Ca, Zn or Al.

14. Containing agents according to claim 12 or 13

• a) 0.01 to 10 wt .-% acid.

15. Composition according to one of claims 12 to 14 containing

• a) 0.01 to 40% by weight of conventional additives,
• b) 50 to 95 wt .-% water.